GB2064367A - Semi-permeable Composite Membrane - Google Patents
Semi-permeable Composite Membrane Download PDFInfo
- Publication number
- GB2064367A GB2064367A GB7941721A GB7941721A GB2064367A GB 2064367 A GB2064367 A GB 2064367A GB 7941721 A GB7941721 A GB 7941721A GB 7941721 A GB7941721 A GB 7941721A GB 2064367 A GB2064367 A GB 2064367A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composite membrane
- high performance
- polyamine
- group
- membrane according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 239000010410 layer Substances 0.000 claims abstract description 76
- 230000004888 barrier function Effects 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000013047 polymeric layer Substances 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 229920000768 polyamine Polymers 0.000 claims description 56
- 229920000620 organic polymer Polymers 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 125000003277 amino group Chemical group 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 229920002492 poly(sulfone) Polymers 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000012695 Interfacial polymerization Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WJUBYASTGWKFHK-UHFFFAOYSA-N azepan-3-amine Chemical compound NC1CCCCNC1 WJUBYASTGWKFHK-UHFFFAOYSA-N 0.000 claims description 4
- OROOBNKHDZYDFL-UHFFFAOYSA-N n-methylazepan-3-amine Chemical compound CNC1CCCCNC1 OROOBNKHDZYDFL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 4
- 150000002367 halogens Chemical group 0.000 claims 4
- 238000003490 calendering Methods 0.000 claims 3
- 239000004745 nonwoven fabric Substances 0.000 claims 3
- 239000002759 woven fabric Substances 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 150000004820 halides Chemical class 0.000 claims 2
- 229920000098 polyolefin Polymers 0.000 claims 2
- 239000012779 reinforcing material Substances 0.000 claims 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- 239000011253 protective coating Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 amine compound Chemical class 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 238000001223 reverse osmosis Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 229940012017 ethylenediamine Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012696 Interfacial polycondensation Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- BXJAXTLXMBZUHS-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride;hexane Chemical compound CCCCCC.ClC(=O)C1=CC=CC(C(Cl)=O)=C1 BXJAXTLXMBZUHS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- GPCKFIWBUTWTDH-UHFFFAOYSA-N pentane-3,3-diamine Chemical compound CCC(N)(N)CC GPCKFIWBUTWTDH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
- B01D71/601—Polyethylenimine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A high performance semipermeable composite membrane containing a microporous substrate. An intermediate transport polymeric layer comprising a feed cross-linked water-soluble polymer formed thereof and an ultrathin solute barrier layer comprising (1) an inner portion affixed to the transport layer and comprising a cross-linked polymer and linear polymer which comprises the reaction product of the polymer and the monomer used in the transport layer and an outer portion comprising the reaction product of the transport layer with a cross-linking agent.
Description
SPECIFICATION
Semipermeable Composite Membrane
This invention relates to a high performance membrane and to a process for producing the same, and relates particularly to a novel and highly advantageous semipermeable composite membrane having a high percentage solute rejection and which is especially useful for production of pure water from sea water, which is useful for recovery of valuable materials, and which has excellent resistance to degradation in the presence of chlorine.
Background of the Invention
In recent years liquid separation and purification systems utilizing reverse osmosis have been applied in many fields such as the desalination of sea water or other saline waters and in the recovery of valuable materials from waste liquids of various types.
Various semipermeable membranes are now being used in commercial reverse osmosis treatments of aqueous solutions, either for water purification or for concentration of liquid solutions, or both. Such semipermeable membranes include the early Loeb type membranes made of cellulose acetate by processes as described in U.S. Patents Nos. 3,133,132 and 3,133,137. The Loeb type membranes are asymmetric types and are characterized by a very thin, dense surface layer or skin that is supported upon an integrally attached, thicker supporting layer. However, the cellulose acetate Loeb type membranes are restricted as to use and as to processability, largely because the membranes must be kept wet at all times; their effectiveness as reverse osmosis membranes is lost once the membranes are dried.
These membranes have also exhibited deficiencies such as alkaline or acidic degradation and biological degradations which result in short life. Furthermore, these membranes are not used widely in separation or recovery of valuable materials from liquid mixtures containing organic chemicals, because the membranes have low selectivity for valuable organic materials and poor resistance to the effects of organic solvents.
Other Loeb type membranes which are also used include membranes fabricated from polyamides (please refer to U.S. Patent No. 3,567,632, for example), polyamide hydrazide, polyamide acid (Japanese Patent Publication No.50-121, 168) crosslinked polyamide (Japanese Patent Publication
No. 52--152, 879), polyimidazopyron, polybenzimidazole, polysulfonamide,-polybenzimidazolon, polyaryleneoxide, polyvinylmethylether, polyacrylonitril, polyvinylalcohol, polyhyd roxethyl methacrylate and polyvinylidinechloride, etc. However, the separation performances and the resistances to chemical degradation of these Loeb type membranes are all inferior to those of the cellulose acetate membranes.
When utilizing the semipermeable membranes in the treatment of brackish water, particularly the treatment of sea water, it is often necessary to treat the feed materials with chlorine or other oxidizing agents so as to guard against bacterial growth which could greatly deter the performance of the membranes as a result of fouling or the like. Therefore, this chemical degradation in the membranes results in too short a useful life, with accompanying too-low salt rejection, which results in an inefficient operation.
In a later development, processes have been provided for preparing an ultra-thin film or skin separately from a porous supporting layer.
Membranes so prepared have become known as composite membranes. In preparing such membranes it is possible to tailor both the ultra-thin film and the porous supporting layer in such a manner that each component possesses the most desirable properties. Processes for preparation of composite membranes are described in U.S. Patents Nos. 3,744,642 and 3,926,798 and in P.B.
Reports Nos. 234,198 and 248,670.
Generally, these composite membranes have also exhibited deficiencies such as compaction resulting in short life, as well as undesirably low flux or solute rejection, all resulting in inefficient operation.
Summary of the Invention
It is an object of this invention to provide a semipermeable composite reverse osmosis membrane which provides at least 99.5% of solute rejection and has excellent resistance to chlorine, Another object of this invention is to provide a composite membrane which is not only capable of production of pure water from sea water but is useful for the recovery of valuable materials from the water as well. A further object of this invention is to provide a method for making such a composite membrane which can be produced in simple steps which lends itself favorably to commercial production.
Yet another object is to provide a method of controlling membrane thickness of an ultrathin membrane to thereby provide membranes of predetermined thickness ideally adaptable for usage under a wide variety of pressure conditions in service.
Other objects and advantages of this invention will appear in further detail hereinafter.
Detailed Description of the Invention
In accordance with this invention, a semipermeable composite membrane is provided comprising a microporous substrate and a semipermeable membrane formed on a surface of the microporous substrate. The semipermeable membrane is composed of a crosslinked polymer made by reacting (a) a mixture containing a water soluble organic polymer having reactive groups in terminal and or side chains of the organic polymer, said mixture also containing a reactive monomer or amine, with (b) a cross-linking agent having a polyfunctional group capable of reacting with the reactive groups of the water soluble organic polymer and also of reacting with the monomer or polyamine contained in the mixture (a).The mixtures (a) and (b) are essentially immiscible with one another whereby interfacial polymerization takes place among the water soluble organic polymer, the monomer or amine. and the crosslinking agent to form an ultrathin layer. At the same time, some of the monomer or amine migrates through the ultrathin layer and polymerizes with the cross-linking agent to form an outer, cross-linked or non-cross-linked polymeric ultrathin outer portion on the aforementioned ultrathin layer.
By performing the polymerization of the water-soluble polymer in an interfacial manner the resulting polymer forms an ultrathin solute rejection barrier of surprising uniformity with respect to thickness. Further, by predetermining the amount and type of monomer or polyamine present in the aqueous polymer solution the amount penetrating through the aforesaid ultrathin barrier is also predetermined, and this predetermines the thickness of the further ultrathin barrier portion that will be produced from polymerization of the monomer or polyamine with the cross-linking agent. In this surprising and highly effective manner the overall thickness of the ultrathin solute rejection barrier can be accurately predicted, and the uniformity of thickness of the resulting barrier is entirely unprecedented.
Thickness control is highly important because solute rejection barriers are utilized under various pressures in different fields of service. Where low values of solute rejection are sufficient, very thin barriers (100 or less) may be used at low pressures. On the other hand, barriers as thick as 1,000A or more may be provided in accordance with this invention, and these may be used under very high pressure with adequate solute rejection performance.
Examples of water soluble organic polymers which are useful in the practice of this invention include amine modified polyepihalohydrin, polyethyleneimine and polyepiaminohydrin, preferably, water soluble reaction products which are obtained by reacting an amine compound with a polyepihalohydrin represented by the following Formula
wherein X is a halogen atom such as Cl, Br or I, and i and j are mole fractions and satisfy the following relations:
i+j=l O < i~1 0 < j < 0.8 The amine compound (II) which is used with the organic polymer in the practice of this invention preferably fulfills the following requirements:
(II) It is a non-cyclic or cyclic monomeric polyamine containing::
1) from 0 to 1 amino group;
2) more than one imino group and
3) the sum of the amino and the imino groups is more than two, wherein the amino group, if
present, is bonded to a carbon atom or to two different carbon atoms, the total number of
carbon atoms being 3 to 12.
Examples of polyepihalohydrins represented by Formula (I) include polyepichlorohydrin, polyepibromohydrin and polyepiiodohydrin. Examples of the polyamines (II) include piperazine, 2,5- dimethylpiperazine, 4-aminomethylpiperizine, 3-aminohexahydroazepine, 3- methylaminohexahydroazepine, monomethylethylenediamine, N,N-dimethylethylenediamine and mono-N-methyldiethylenetriamine.
These polyepihalohydrins may be modified by reacting them with the aforementioned amine compounds according to the procedure well known in prior art, for example, as described in U.S. Patent
No. 4,056,510. Examples of polyamines being mixed with water soluble organic polymers having amino groups are preferably the aforementioned amine compounds, although other polyamines such as ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diethylenetriamine, dipropylenetriamine, triethylenetriamine, pentaethylenehexamine and the like may also be used.
The mixture used for preparing the composite membrane of this invention is obtained by mixing the polyamine and the water soluble organic polymer having amino groups with each other. However, an amine modified polyepihalohydrin containing unreacted monomeric polyamine should be used, so that the reaction mixture of the polyepihalohydrin contains excess polyamine.
The mix ratio of the polymer with the polyamine is about 10% to 90% by weight of polyamine in 90 to 10% by weight of polymer, preferably from about 20% to 85% by weight of polymer and about 80% to 15% by weight of polyamine. When the mix ratio is substantially outside the 90%-1 0% ratio, the resulting composite membrane shows lower solute rejection or lower flux.
As will be described hereinafter, the semipermeable composite membrane of this invention comprises two crosslinked polymers one is obtained by reacting the mixture with a polyfunctional reagent and another is obtained by heat-crosslinking of the water soluble polymer. The semipermeable composite membrane obtained from the crosslinked polymers have the fine structure of a two phase system, that is, an ultrathin solute barrier layer and a intermediate transport layer.
It is considered that the ultrathin solute barrier layer which determines and controls the solute rejection or permeability of the composite membrane, and that the intermediate transport layer is the layer adhering the ultrathin solute barrier to the microporous substrate.
When a membrane is prepared by using only the polyamine, a fine structure attributable to the use of the two phase system does not form in the resulting semipermeable membrane, and the composite membrane does not have good separation performance. On the other hand, when a membrane is prepared by using only a water soluble organic polymer having amino groups (without the monomeric polyamine), the membrane formed does have the fine structure of a two phase system, but the liquid separation performance of the resulting composite membrane is poor. Further, such membranes particularly deteriorate with lapse of time, because the ultrathin solute barrier layer of the semipermeable membrane is very thin and is prone to mechanical damage.
The thickness of the ultrathin solute barrier layer and the intermediate transport layer of the membrane may be controlled in a highly effective manner by altering the mix ratio of the polyamine to the organic polymer. The performance of the composite membrane can be controlled to some degree by altering the thicknesses of the ultrathin solute barrier layer and the intermediate transport layer. The thickness of the ultrathin solute barrier layer is preferably within the range of about 10 A to about 1 more preferably from about 50A to 500A, and the thickness of the intermediate transport layer is preferably in the range of about 1 ooA to 3 microns, more preferably about 0.5 microns to about 2 microns.When the ultrathin solute barrier layer is less than about 1 oA in thickness, the composite membrane is prone to mechanical damage, and it is difficult to retain the separation performance of the membrane.
On the other hand, when the ultrathin solute barrier layer is thicker than about 1,good, the liquid permeation of the composite membrane decreases. Furthermore, when the thickness of the intermediate transport layer is outside the above ranges, the composite membrane has reduced liquid separation performance or undergoes a performance change, because the thickness of the intermediate transport layer is somewhat prone to unevenness and irregulgrity on the surface of the microporous substrate.
Expressed as the sum of the thicknesses of the ultrathin solute barrier layer and the intermediate transport layer, the thickness of the semipermeable composite membrane is preferably about 1 ooA to about 3 microns.
Fig. 1 is an electron microphotograph showing the fine structure of an ultrathin cross section of a semipermeable composite membrane comprising one example in accordance with this invention.
This figure clearly indicates the fine structure of the membrane surface as examined with the aid of an electron microscope. The membrane surface was shadowed with Pt-Pd and carbon in a vacuumdepositing apparatus, and the polysulfone substrate portion of the membrane was dissolved in chloroform. The membrane was embedded with an epoxy resin, dyed with an Oslo, solution and was sectioned by using an ultrathin membrane with a diamond knife. The ultrathin membrane layer of approximately 300A thickness and the supporting layer of about 1 y thickness were examined by a Hitachi HU-12 Transmission Electron Microscope.
Fig. 2 is an electron microphotograph similar to Fig. 1 showing the fine structure of an ultrathin cross section of a semipermeable composite membrane obtained by using a solution containing only the amine modified polyepihalohydrin. The magnifications of the microphotographs of Figs. 1 and 2 are about 90,000 times for each. The microphotographs show that the ultrathin solute barrier layer of the membrane of Fig. 1 is significantly thicker than the ultrathin solute barrier layer of Fig. 2.
Fig. 3 is a schematic cross-sectional drawing, highly enlarged, showing further details regarding the nature of the ultrathin solute barrier layer and the manner in which it is formed.
Fig. 4 is a schematic drawing similar to Fig. 1 but on a less enlarged scale, showing a barrier of this invention in combination with a polysulfone substrate and a fabric.
The interfacial polycondensation method, itself well known, is used for fabrication of the semipermeable composite membranes of this invention. The method has been described in great detail by P. W. Morgan in "Condensation Polymers by Interfacial and Solution Methods", Intersciences
Publishers, New York, 1965.
According to this method, the aqueous mixture of the water soluble organic polymer having amino groups and the monomeric polyamine is coated on a surface of the microporous substrate: thereafter the hydrophobic solution containing polyfunctional reagents whose functional groups are capable of reacting with the amino groups is coated upon but does not mix with the aqueous solution and forms a separate layer thereon. In situ interfacial polycondensation or the microporous substrate takes place between the immiscible solutions and serves to produce an ultrathin surface coating possessing solute barrier characteristics.
Examples of polyfunctional reagents (cross-linking agents) which are useful in the practice of this invention are selected from the group consisting of the acid chlorides such as isophthaloyl chloride.
terephthaloyl chloride, trimesoyl chloride, etc., of isocyanates such as toluylene diisocyanate.
naphthalene diisocyanate, etc., and active halogen compounds such as cyanuric chloride, for example.
They are dissolved in suitable solvents which are substantially immiscible with water, such as hexane, heptane, pentane, benzene, carbon tetrachloride, etc.
The microporous substrate may be formed as a flat sheet or as a tubular or hollow fiber, or in any other desired shape usually used for reverse osmosis separation processes; and the pores in the surface are preferably sized between about 1 oA and about 1ooA. The pores tend to become gradually enlarged toward the back (supporting substrate) side. The aforementioned microporous substrate may be distinguished as an anisotropic membrane made from homopolymers or from mixed polymers of polysulfone, chlorinated polyethylene, polyvinylchloride, cellulose acetate, cellulose nitrate, etc. The most preferable material is polysulfone. Preparation of polysulfone substrates is described in "Office of
Saline Water Research and Development Progress Report" No. 359, Oct., 1968.
The aforementioned characteristic two phase system of the semipermeable membrane of this invention, composed of an ultrathin solute barrier layer and an intermediate transport layer can be obtained by using an aqueous solution containing a water soluble organic polymer having amino groups and a polyamine, in which the concentration of the aforementioned polymer is preferably from about 0.1% to 10% by weight, more preferably from 0.5% to 5% by weight. The concentration of the polyamine is preferably in a range of about 0.1% to 10% by weight, more preferably about 0.5% to 5% by weight. As the result of these concentrations, a two-phase system having the desired thickness can be readily and conveniently obtained. From this a composite membrane possessing excellent separation characteristics can be fabricated with good yield.By simply increasing the polyamine content in the solution the thickness of the resulting ultrathin barrier may also be increased.
The water soluble organic polymer having amino groups and the polyamine in the aqueous solution are converted to a water insoluble crosslinked polymer by interfacial reaction with the polyfunctional reagent contained in the hydrophilic phase. For this reaction one of a number of alkaline reagents, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc., may be added to remove by-products of the reaction, such as hydrogen chloride, etc. Further, catalysts such as crown ethers may be used for acceleration of the reaction. On the other hand, the optimum concentration of the polyfunctional reagent in the water immiscible solution is affected by the concentration of the water soluble organic polymer having amino groups and the polyamine in the aqueous phase. The preferable concentration is between about 0.1% to 10% by weight.
The microporous substrate convered with the ultrathin solute barrier layer, formed by the interfacial condensation reaction, is the cured at a high temperature, which should not be so high as to break the microporous substrate. The temperature is preferably between 800C and 150 C. As a result of this curing, the intermediate transport layer of the water soluble organic polymer of the aqueous phase becomes water insoluble, forming an intermediate transport layer between the ultrathin barrier and the substrate. The semipermeable ultrathin composite membrane becomes stabilized as to durability and separation characteristics. The ultrathin solute barrier layer is formed by an interfacial condensation between the mixture of water soluble organic polymer having amino groups and the polyamine, and the polyfunctional reagent.
When the water soluble organic polymer having amino groups is the only species in the water solution, the ultrathin solute barrier layer formed in the same manner is not more than about 1 ooh in thickness. On the other hand, when the monomeric polyamine is the only species present, the ultrathin solute barrier layer attains a thickness of only a few microns as a maximum. Accordingly, the resulting semipermeable composite membranes are of only very limited use in either case.
In contemplating the nature of the interfacial reaction, and in considering the reactivity and the molecular size of the water-soluble organic polymer having amino groups and the polyamine, the ultrathin solute layer may be formed immediately after contact with the polyfunctional reagents, accompanied or followed by diffusion of the monomeric polyamine only (but not the polymer) through the ultrathin layer. Having penetrated the ultrathin layer, the monomeric polyamine reacts with the polyfunctional reagent contained in the hydrophobic phase and thus forms additional polymer which is deposited upon the ultrathin solute barrier and increases its thickness accordingly.
Because of this phenomenon, the resulting thickness of the ultrathin solute barrier layer of this invention is greater than in the case of using only the water soluble organic polymer having amino groups. Also, such layer is thinner than one produced by the use of polyamine only.
The outer protective layer later applied to the ultrathin solute barrier layer causes the composite membrane to be much more stable against mechanical shocks. Water soluble organic polymers such as polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylamide and polyacrylic acid, for example, are useful in forming the protective layer. Addition of a polyfunctional halogenated compound to this water solution is sometimes useful for crosslinking the protective layer, resulting in good water resistance. The remaining polyfunctional reagents of the interfacial polycondensation on the ultrathin solute barrier layer are also useful for crosslinking the protective layer.The optimum thickness of the protective layer is about 0.1 mm to 20 millimeters when PVA or PVP is used:
Fig. 3 of the drawings shows diagrammatically and greatly magnified itypical structure obtained according to this invention. The intermediate transport layer 10 is composed of water-insoluble polymer formed from the water-soluble polymer of the aqueous layer which remains it place on the polysulfone substrate 11 and which was solidified and rendered water-insoluble by heatitsg. Next to the intermediate transport layer 10 is the composite ultrathin solute rejection barrier 12; its inner layer 13 is formed by reaction of the water-soluble polymer plus the monomeric polyamine with the crosslinking agent: a cross-linked product of all three.During these reactions the monomeric polyamine also migrates in the direction of the arrow in Fig. 3 from the aqueous phase through the barrier layer 13 formed at the interface, and reacts with the cross-linking agent of the organic phase, producing the outer layer 14 of the ultrathin solute rejection barrier. This outer layer 14 is the cross-linked product of the monomeric polyamine (but not the polymer) or non-crosslinked with the cross-linking agent. The number 15 designates the outer protective layer preferably subsequently applied.
Fig. 4 shows the polysulfone substrate 11 supported by a fabric 16. This figure also shows the typically irregular surface 17 of the polysulfone substrate 11, which is difficult to coat with a uniformly thick coating. The intermediate transport layer 10 admirably compensates for this surface roughness and securely attaches itself to the polysulfone layer while also providing an excellent, much more uniform supporting surface for the ultrathin solute barrier layer 12. In this manner thickness variations of the layer 12 are minimized. For example, in a typical case a layer 12 may be provided with a maximum thickness of 500A and a minimum thickness of 200A, which is highly significant in terms of barrier performance.
The following specific Examples have been selected as illustrative of various ways in which this invention may be practiced. They are not intended to define or to limit the scope of the invention, which is set forth in the appended claims.
Example 1
120 grams of sodium iodide were dissolved in 80 grams of hot methylethylketone. To this,92.5 grams of polyepichlorohydrin dissolved in 200 grams of methylethylketone were added, and the product was stirred at the boiling temperature for 25 hours. The resulting solution was cooled to room temperature, filtered and 3,000 grams of water were added. The precipitated polymer was washed in 500 grams of methanol and dried in vacuum at 5000 for 10 hours to obtain a polyepiiodohydrin. 80% of chloro groups were found to be changed to iodo groups from chemical analysis. 12 grams of polyepiiodohydrin were dissolved in 100 grams of tetrahydrofuran and 10 grams of water and 35 grams of 4-(aminomethyl) piperizine were added.After stirring at 3500 for 6 hours, sulfuric acid was added dropwise to neutralize the resultant solution. 300 grams of methanol were added to the resulting solution, and a white precipitate was obtained. This precipitate was purified by use of four reprecipitations, each from a methanol and water solution (methanol/water=3/1). The product was then passed through an anionic ion exchange resin bed to remove the sulfuric acid base, and the polymeric substance was obtained. From the results of infrared spectrum analysis and 13C nuclear magnetic resonance, this polymer was found to be 4-(aminomethyl)piperizine modified with polyepiiodohydrin.
This polymer was stored in a refrigerator as a water solution. A water solution containing 1.5% of 4-(aminomethyl)piperizine modified polyepiiodohydrin and 0.5% of 4-(aminomethyl)piperizine and a hexane solution containing 0.2% of isophthaloyl chloride were prepared.
The water solution was poured on the flat surface of a polysulfone microporous substrate, which was then placed in a vertical position for 30 minutes to drain off the excess solution. After this, the hexane-isophthaloyl chloride solution was also poured on the substrate and on top of the aqueous solution, causing interfacial polymerization to occur. After 30 seconds, the excess solution was drained in the same manner for 1 minute.
The membrane was then cured in a convection oven at 12000 for 10 minutes, cross-linking the water-soluble polymer and the monomer. It was cooled at room temperature, and covered by a 1% polyvinylalcohol solution. Excess solution was drained off while maintaining the membrane in a vertical position. The membrane was finally cured at 11000 in an oven for 10 minutes. The reverse osmosis performance of the resulting composite membrane was measured under the following conditions:
Pressure: 56 Kg/cm2
Feed solution: 3.5% NaCI aqueous solution
Temperature: 2500 The composite membrane showed 99.65% salt rejection and 0.35 m3/m2 day water flux.
Example 2
A solution of 12 grams of polyepiiodohydrin in 50 grams of tetrahydrofuran was added to a solution of 35 grams of 4-(aminomethyl)piperizine in 100 grams of tetrahydrofuran and 10 grams of water. The mixture was stirred at 500C for 1 hour. Then the mixture was poured into 500 grams of benzene, after which the precipitate was obtained by decantation washed with benzene several times and dried at 250C for 0.5 hours in vacuum.
The precipitate which contained 4-(aminomethyl) piperizine modified polyepiiodohydrin and excess 4-(aminomethyl) piperizine was dissolved in water to form a 0.5% aqueous solution. The microporous polysulfone substrate which was prepared separately was coated with the aforementioned 0.5% aqueous solution; after that a 0.2% solution of isophthaloyl chloride in hexane was carefully poured on it. The product was cured at 1 200C for 5 minutes to produce a composite membrane. The performance of this membrane was 0.7 m3/m2.day flux and 99.77% salt rejection under the following conditions:
Pressure: 40 Kg/cm2
Feed solution: 0.25% NaCI aqueous solution
Temperature: 250C pH: 7
The feed pH was changed from 7 to 1, then from 1 to 13, and finally from 13 to 7.The membrane performance was changed as follows:
pH Water flux (m3/m2.dat) Salt rejection (O/o/ 7 0.7 99.7
1 0.6 50
13 0.7 98.6
7 0.7 99.7
Examples 3 to 5; Comparative Examples 1 to 2
The mix of polymer and 4-(aminomethyl) piperizine in Example 1 was changed; preparation of the membrane was otherwise the same as in Example 1.
Reverse osmosis performance was measured under the same conditions as in Example 1.
4-{aminomethyl) Polymer Salt (%) Water flux
Examples piperizine { /0) /O/o/ rejection m3/m2. day) 3 0.75 1.25 99.60 0.36
4 1.0 1.0 99.48 0.36
5 1.25 0.75 99.45 0.34
Comparative
Examples
1 0 2 92.0 0.51
2 2 0 30.0 0.15
Example 6
Figure 1 of the drawings represents an electron-microphotograph of the cross section of the composite membrane obtained in Example 1.
The polyvinylalcohol protective layer, the ultrathin solute barrier layer, the intermediate transport layer were observed as in Figure 1.
Example 7
The composite membrane obtained from Example 1 was tested under the following conditions:
Pressure: 56 Kg/cm2
Feed solution: sand filtered seawater
Temperature: from 150C to 250C Salt rejection (%) Water flux (m3/m2.day)
after 10 hours 99.62 0.34
after 1,000 hours 99.61 0.32
Then 0.1 ppm of chlorine was added to the feed and the test was continued for 60 hours. The salt rejection value was reduced to 99.58% and the water flux value was reduced to 0.25 m3/m2.day. After this the chlorine addition was stopped and the test was continued for 50 additional hours. The salt rejection and flux values were found to have recovered to 99.60% and 0.31 m3/m2.day, respectively.
Example 8
Stability in hot water and strength for high pressure operation were measured by using the membrane obtained from Example 2 under the following conditions:
Pressure: 70 Kg/cm2
Feed: Synthetic sea water
Temperature: 400C
Operating times: 300 hours
,
Salt rejection (%) Water fA,us #m3/m2.day) 24 hrs. after start 99.43 0.40 of operating
300 hrs. after start 99.36 0.36
of operating
Examples 9 to 11 and Comparative Examples 3 to 5 Piperazine, 3-(methylamino)hexahydroazepine and 3-(amino) hexahydroazepine were used instead of the 4-(aminomethyl)piperizine of Example 3 and of Comparative Example 2.
Salt Water
Examples Polyamine Polymer Rejection m3/m2.day) 9 piperazine same as Ex. 1 95.0 0.35
10 3-(methylamino) same as Ex. 1 98.2 0.33
hexahydroazepine
11 3-(amino)hexahydro- same as Ex. 1 99.3 0.28
azepine
Comparative Salt Water flux
Examples Polyamine Polymer Rejection m3/m2. day) 3 piperazine none 75.2 i 0.03
4 3-(methylamino)- none - nearly 0
hexahydroazepine
5 3-(amino)hexa- none 42.3 0.04
hydroazepine
Example 12 and Comparative Example 6
An aqueous solution containing 2% polyethyleneimine and an aqueous solution containing 1.2to polyethyleneimine and 0.8% 4-(aminomethyl)piperizine were prepared.
The performance of the membrane made from these solutions, prepared as in Example 1 , was measured under the conditions of 40 Kg/cm2,0.25% NaCI aqueous solution at 250C.
4-(aminomethyl)- Salt Water flux
Example Polyethyleneimine piperizine rejection (m3/m2. day) 12 1.2 0.8 99.6 0.40
Comparative
Example
6 2 ~ 97.8 0.52
Example 13 and Comparative Example 7
Polyepichlorohydrin was treated with NaN3 to obtain polyepiazidohydrin, and was then reduced by LIAIH, to obtain polyepiaminohydrin.
An aqueous solution containing 0.6% polyepiaminohydrin and 0.4% piperazine and an aqueous solution containing 1% polyepiaminohydrin were prepared, respectively.
The performances of the membranes made from these solutions prepared as in Example 1 were measured under the following conditions:
Pressure: 40 Kg/cm2
Feed: 0.25% NaCI
Temperature: 250C
Salt rejection Water flux
Example Polyepiaminohydrin Piperazine (%) (m3/m2. day)
13 0.6 0.4 99.66 0.40
Comparative
Example
7 1.0 - 97.8 0.52
Example 14 and Comparative Example 8
An aqueous solution containing 1.2% "EPIAMINE" (made by Dow Chemical Co., ethylene diamine modified polyepichlorohydrin) and 0.8% ethylene-diamine, and an aqueous solution containing 2% "EPIAMINE" were prepared, respectively. The membranes were fabricated as in Example 1. They showed the performance parameters set forth below, under the same conditions as in Example 13.
Salt rejection Water flux
Example "EPlAMINE" Ethylenediamine (%) (m3/m2. day) 14 1.2 0.8 99.64 0.11
Comparative
Example
8 2.0 ~ 98.7 0.11
Fig. 2 is an electronmicrophotograph showing the fine structure of the ultrathin cross section of the membrane obtained from Comparative Example 8. The ultrathin solute barrier layer of the membrane is thinner than the membrane of Example 1.
Although this invention has been shown and described with reference to specific examples thereof, many variations may be practiced. For example, the monomeric migration mechanism described in detail herein may be utilized with various chemical structures, so long as the monomer has the capability of penetrating through the barrier to react with further cross-linking agent.
Further, it will now be apparent that the hydrophilic and hydrophobic layers may be reversed, with the organic layer directly applied to the substrate and the aqueous layer applied thereon. Also, while reference has been made to polysulfone as the preferred substrate, other substrates may be substituted.
Other variations may be made, including substitution of equivalents, reversals of steps, and the use of certain features independently of other features, all as set forth in the appended claims.
Claims (32)
1. A high performance semipermeable composite membrane comprising (a) a microporous substrate, (b) an intermediate transport polymeric layer comprising a heat-crosslinked water-soluble polymer formed upon and affixed to said microporous substrate, (c) an ultrathin solute barrier layer comprising (i) an inner portion affixed to said intermediate transport layer and comprising a crosslinked polymer and linear polymer which comprises the reaction product of the polymer and the monomer used in the intermediate transport layer (b) with a cross-linking agent and (ii) an outer portion comprising the reaction product of the monomer of intermediate transport layer (b) with a cross-linking agent.
2. The membrane defined in Claim 1, wherein said layer (c) has a controlled and substantially uniform thickness of about 10 to 1,good.
3. A high performance semipermeable composite membrane comprising a microporous substrate having a semi-permeable membrane on the surface thereof, the semipermeable membrane being composed of a cross-linked polymer comprising the reaction product of a mixture of (a) a water soluble organic polymer having reactive amino groups in terminal and/or side chains of the organic polymer, (b) a polyamine, and (c) a cross-linking agent having a group capable of reacting with the reactive groups of the water soluble organic polymer and also of reacting with the polyamine, and reacting said polyfunctional group with the amino groups of said organic polymer and with said polyamine.
4. A high performance semipermeable composite membrane according to Claim 3, wherein the water soluble organic polymer has amino groups selected from the group consisting of amine modified polyepihalohydrin, polyethyleneimine and polyepiaminohydrin.
5. A high performance semipermeable composite membrane according to Claim 3, wherein the polyamine is selected from the group consisting of cyclic or non-cyclic amino compounds containing from 2 to about 12 carbon atoms.
6. A high performance semipermeable composite membrane according to Claim 4, wherein the amine modified polyepihalohydrin is a modified polymer made by reacting at least one polyopihalohydrin represented by the Formula (I):
wherein the X is halogen selected from the group consisting of Cl, Br and I, and i and j are mole fractions and satisfy the following relationships:
i+j=1 0 < i < 1 O < j < 0.8 with at least one polyamine (II) which is a non-cyclic or cyclic polyamine containing:
1) from 0 to 1 amino group.
2) more than 1 imino group, and
3) the sum of the amino and the imino group(s) is more than 2, wherein the amino group when
present is bonded to a carbon atom and the imino group is bonded to a carbon atom or to two
different carbon atoms, the total number of carbon atoms being from 3 to 12.
7. A high performance semipermeable composite membrane according to Claim 6, wherein the polyamine mixed with the amino modified polyepihalohydrin is at least one of said polyamines (íí) defined in Claim 4.
8. A high performance semipermeable composite membrane according to Claim 6, wherein the polyamine (II) is selected from the group consisting of 4-aminomethylpiperizine, piperazine, 2,5- dimethylpiperazine, 3-methylaminohexahydroazepine and 3-aminohexahydroazepine.
9. A high performance semipermeable composite membrane according to Claim 3, wherein the cross-linking agent has a polyfunctional group selected from the group consisting of acid halides, organic isocyanates and activated halogens having at least two functional groups.
10. A high performance semipermeable composite membrane according to Claim 9, wherein the polyfunctional reagent is selected from the group consisting of isophthaloyl chloride, terephthaloyl chloride, trimesoyl trichloride, toluylene diisocyanate, naphthalene diisocyanate and cyanuric chloride.
11. A high performance semipermeable composite membrane according to Claim 3, wherein the ratio of contents of the mixture is in the range of about 10% to about 90% by weight of the water soluble organic polymer and about 90% to 10% by weight of the polyamine.
12. A high performance semipermeable composite membrane according to Claim 3, wherein the semipermeable membrane has a laminated structure consisting of an ultrathin solute barrier layer and an intermediate transport layer.
13. A high performance semipermeable composite membrane according to Claim 3, wherein the semipermeable membrane has a thickness of about 1 ooA to about 3y.
14. A high performance semipermeable composite membrane according to Claim 12, wherein the ultrathin solute barrier layer has a thickness of about 1 oA to about 1000a and the intermediate transport layer has a thickness of about 100 to about 3,u.
15. A high performance semipermeable composite membrane according to Claim 3, wherein the microporous substrate comprises an organic polymer selected from the group consisting of polysulfone, chlorinated polyolefine, cellulose acetate and polyvinylchloride.
16. A high performance semipermeable composite membrane according to Claim 3, wherein the microporous substrate is reinforced by a reinforcing material selected from the group consisting of calendered woven or non-woven fabric, uncalendered woven or non-woven fabric, porous film and paper.
17. A high performance semipermeable composite membrane according to Claim 3, wherein the semipermeable membrane is protected by a crosslinked polymer selected from the group consisting of polyvinylalcohol, partially saponified polyvinylacetate and polyvinylpyrrolidone.
18. A high performance semipermeable composite membrane according to Claim 17, wherein the protective coating has a thickness of about 1 ,oooA to about 10 microns.
19. A process for producing a high performance semipermeable composite membrane comprising the steps of:
(a) covering the surface of a microporous substrate with an aqueous solution containing at least one water soluble organic polymer having reactive groups in terminal and/or side chains of the organic polymer, said aqueous solution also containing a reactive monomer or polyamine,
(b) covering the resulting coated porous substrate with a solution which is substantially immiscible with the solution of step (a) and which contains a polyfunctional reagent capable of undergoing interfacial polymerization with said reactive groups of the water soluble organic polymer and with said reactive monomer or polyamine to form an ultrathin film on said surface of said microporous substrate,
(c) containing said interfacial polymerization reaction for a time sufficient to cause migration of at least a portion of said monomer or polyamine through the ultrathin film, thereby reacting said monomer or polyamine with said polyfunctional reagent to form a further ultrathin polymeric layer on the ultrathin layer being formed, and
(d) drying the resulting composite semipermeable membrane at an elevated temperature for a time sufficient to polymerize said water soluble organic polymer.
20. A process for producing a high performance semipermeable composite membrane comprising the steps of:
(a) treating a microporous substrate with an aqueous solution containing at least one water soluble organic polymer having reactive amino groups in terminal and/or side chains of the organic polymer, said solution also containing a monomeric polyamine,
(b) applying to the resulting coated porous substrate a solution which is essentially immiscible with the solution used in step (a) and containing a polyfunctional reagent capable of reacting with said reactive amino groups of the water soluble organic polymer and with the polyamine to form an ultrathin film on one surface of the microporous substrate, and
(c) drying the resulting composite semipermeable membrane at an elevated temperature.
21. A process according to Claim 20, wherein the water soluble organic polymer is selected from the group consisting of amine modified polyepihalohydrin, polyethyleneimine and polyepiaminohydrin.
22. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the polyamine is selected from the group consisting of cyclic and/or non-cyclic amino compounds containing from 2 to about 12 carbon atoms.
23. A process for producing a high performance semipermeable composite membrane according to Claim 21, wherein the amine modified polyeiphalohydrin is a modified polymer made by reacting at least one polyepihalohydrin represented by the following Formula (I):
wherein X is halogen selected from the group consisting of Cl, Br, and I, and i and j are mole fractions and satisfy the following relationships:
i+j=1 O < i < 1 O~j < 0.8 with a polyamine (II) which is a non-cyclic or cyclic polyamine containing::
1) from O to 1 amino group,
2) more than 1 imino group, and
3) the sum of the amino and the imino groups is not more than 2 wherein the amino when
present is bonded to a carbon atom and the imino group is bonded to a carbon atom or to two
carbon atoms, the total number of carbon atoms being from 3 to 12.
24. A process for producing a high performance semipermeable composite membrane according to Claim 23, wherein the polyamine mixed with the amine modified polyepihalohydrin is at least one of the polyamines (II) defined in Claim 23.
25. A process for producing a high performance semipermeable composite membrane according to Claim 23, wherein the polyamine is selected from the group consisting of 4-aminomethylpiperizine, piperazine, 2,5-dimethylpiperazine, 3-methylaminohexahydroazepine and 3-aminohexahydroazepine.
26. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the polyfunctional reagent is selected from the group consisting of acid halides, organic isocyanates and activated halogens having at least two functional groups.
27. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the polyfunctional reagent is selected from the group consisting of isophthaloyl chloride, terephthaloyl chloride, trimesoyl trichloride, toluylene diisocyanate, naphthalene diisocyanate and cyanuric chloride.
28. A process for producing a high performance semipermeable composite membrane according to Claim 17, wherein the ratio of contents of the mixture is in the range of about 10% to about 90% by weight of the water soluble organic polymer and about 90% to 10% by weight of the polyamine.
29. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the concentration of the aqueous solution is in the range of about 0.1% to 10% by weight.
30. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the concentration of the polyfunctional reagent solution is in the range of about 0.19/0 to 10% by weight.
31. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the microporous substrate comprises an organic polymer selected from the group consisting of polysulfone, chlorinated polyolefine, cellulose acetate and polyvinyl-chloride.
32. A process for producing a high performance semipermeable composite membrane according to Claim 20, wherein the microporous substrate is reinforced by a reinforcing material selected from the group consisting of calendered or non-calendered woven or non-woven fabric, porous film and paper.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7941721A GB2064367B (en) | 1979-12-04 | 1979-12-04 | Semi-permeable composite membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7941721A GB2064367B (en) | 1979-12-04 | 1979-12-04 | Semi-permeable composite membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2064367A true GB2064367A (en) | 1981-06-17 |
GB2064367B GB2064367B (en) | 1984-02-29 |
Family
ID=10509585
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7941721A Expired GB2064367B (en) | 1979-12-04 | 1979-12-04 | Semi-permeable composite membrane |
Country Status (1)
Country | Link |
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GB (1) | GB2064367B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0056512A1 (en) * | 1981-01-15 | 1982-07-28 | Brunswick Corporation | Reverse osmosis membrane and process for making the same |
EP0072002A1 (en) * | 1981-08-07 | 1983-02-16 | Toray Industries, Inc. | High performance semipermeable composite membrane and process for producing same |
EP0085111A1 (en) * | 1981-08-03 | 1983-08-10 | Teijin Limited | Composite semipermeable membrane, process for its production, and method of its use |
EP0117919A2 (en) * | 1982-12-24 | 1984-09-12 | Toray Industries, Inc. | A membrane treatment method for semipermeable membranes |
EP0134055A2 (en) * | 1983-08-02 | 1985-03-13 | Shell Internationale Researchmaatschappij B.V. | Composite dense membrane and fluid(s) separation process carried out therewith |
EP0392982A2 (en) * | 1989-04-14 | 1990-10-17 | Membrane Products Kiryat Weizmann Ltd. | Solvent stable membranes |
US5032282A (en) * | 1989-04-14 | 1991-07-16 | Aligena Ag | Solvent-stable semipermeable composite membranes |
EP2695670A4 (en) * | 2011-04-01 | 2015-05-27 | Toray Industries | Composite semipermeable membrane, composite semipermeable membrane element, and method for manufacturing composite semipermeable membrane |
-
1979
- 1979-12-04 GB GB7941721A patent/GB2064367B/en not_active Expired
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0056512A1 (en) * | 1981-01-15 | 1982-07-28 | Brunswick Corporation | Reverse osmosis membrane and process for making the same |
EP0085111A1 (en) * | 1981-08-03 | 1983-08-10 | Teijin Limited | Composite semipermeable membrane, process for its production, and method of its use |
EP0085111A4 (en) * | 1981-08-03 | 1984-06-29 | Teijin Ltd | Composite semipermeable membrane, process for its production, and method of its use. |
EP0072002A1 (en) * | 1981-08-07 | 1983-02-16 | Toray Industries, Inc. | High performance semipermeable composite membrane and process for producing same |
EP0117919A3 (en) * | 1982-12-24 | 1987-12-16 | Toray Industries, Inc. | A membrane treatment method for semipermeable membranes |
EP0117919A2 (en) * | 1982-12-24 | 1984-09-12 | Toray Industries, Inc. | A membrane treatment method for semipermeable membranes |
EP0134055A2 (en) * | 1983-08-02 | 1985-03-13 | Shell Internationale Researchmaatschappij B.V. | Composite dense membrane and fluid(s) separation process carried out therewith |
EP0134055A3 (en) * | 1983-08-02 | 1988-04-20 | Shell Internationale Research Maatschappij B.V. | Composite dense membrane and fluid(s) separation process carried out therewith |
EP0392982A2 (en) * | 1989-04-14 | 1990-10-17 | Membrane Products Kiryat Weizmann Ltd. | Solvent stable membranes |
EP0392982A3 (en) * | 1989-04-14 | 1991-01-09 | Membrane Products Kiryat Weizmann Ltd. | Solvent stable membranes |
US5032282A (en) * | 1989-04-14 | 1991-07-16 | Aligena Ag | Solvent-stable semipermeable composite membranes |
EP2695670A4 (en) * | 2011-04-01 | 2015-05-27 | Toray Industries | Composite semipermeable membrane, composite semipermeable membrane element, and method for manufacturing composite semipermeable membrane |
US20190070569A1 (en) * | 2011-04-01 | 2019-03-07 | Toray Industries, Inc. | Composite semipermeable membrane, composite semipermeable membrane element, and method of manufacturing composite semipermeable membrane |
Also Published As
Publication number | Publication date |
---|---|
GB2064367B (en) | 1984-02-29 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PE20 | Patent expired after termination of 20 years |
Effective date: 19991203 |